Resolution of hydrocarbon emulsions



Patented Jan. 23, 1940 UNITED STATES RESOLUTION OF HYDROGARBON EMULSIONS Waldemar 0. Mitscherling, Bridgeport, Gonn., as-

signor to The Neon Research Corporation, Bridgeport, Conn, a corporation of Connecticut No Drawing. Application April 20, 1936,

Serial No. 75,416

7 Claims. (ol. 204-24) The invention relates to a process for the treatment or resolution of emulsions. More particu larly, it relates to a procedure whereby 'emulsions of an oil: water, i. e., water-oil and oil- 5 water type, may be de-emulsified, and includes correlated improvements and discoveries whereby obtainment of such a result is enhanced.

The diificulties attendant upon the resolution,

or breaking of various emulsions and especially l water-oil emulsions has been realized for many years, and many and varied attempts have been made to efiect a substantially complete separation of the phases as the oil and the water. A field of activity in which emulsions are markedly l troublesome is the refining of petroleum, and. the

breaking of the emulsions is not only highly desirable, but decidedly important inasmuch .as,

otherwise the production of certain wells may be entirely unusable, and hence of no value, thus 20 entailing a loss to the producer and lack of supply to the refiner.

A considerable number of procedures have been devised for the breaking of water-oil emulsions and of these some are eifective and separate all 25 of the water, whereas others occasion only a partial separation and are thus of little avail inasmuch as a small percentage of water remaining renders many oils incapable of use.

It is a general object of this invention to pro- 30 vide a process in accordance with which the separation of the phases of an emulsion is substantially complete.

A further object of the invention is to provide a procedure whereby the separation or resolution with retention of little or no water in the oil.

A further object of the invention is to provide a process for the resolution of various emulsions which may be readily, effectively, and economically carried out on a commercial basis.

An additional object of the invention is the provision of a process whereby emulsions are resolved by subjecting the emulsion to the influence of effects emanating from a rare gas tube.

A specific object of the invention is to resolve water-oil emulsions by subjecting them to efiects arising from the operation of a positive column argon-neon tube.

50 Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others 55 thereof, which will be exemplified in the process hereinafter disclosed, and the scope of the invention will be indicated in the claims.

In the practise of the invention, an emulsion may be resolved into its phases, i. ve., the disperse phase and the dispersed phase by subjecting the 5 emulsion to effects which arise, or emanate, from an ionized gas tube particularly a positive column tube, and especially a rare gas tube while under the influence of an electrical impress. The tube is preferably a positive column tube and especially a rare gas tube of the hard type; that is, one which vibrates vigorously when operating.- It will be understood, therefore, that the expression hard type used in the specification and claims refers to a tube having strongly vibrating characteristics. a

Further, the tube may be a highly evacuated or low pressure tubehaving, for example, a pressure of about 10 mm. and filled with a mixture containing argon and neon in the ratio of four to one. Argon and neon may be utilized separately as well as in the above stated'combination and others of the rare gases may likewise be employed, a's xenon, krypton, and helium.- Hydrogen also may be utilized as the gas with which the tube is filled. Furthermore, it is desired to point out that the characteristics of the ionized gas tube may be varied depending upon the pressure within thetubep the diameter of the tube, and the presence of other substances, as carbon, mercury, gallium, and sodium. The hardness of the tubes is in relation to the extent to which the gas is ionized, thus the greater the ionization, the greater the hardness.

The emulsion to be resolved is brought into direct contact with the ionized gas orvapor tube and this may be accomplished in any suitable manner, for example, by surrounding the tube with a jacket and conducting the emulsion through said jacket and in contact with the tube. 40

In addition, the efficacy of the gas or vapor tube may, in the absence of considerable amounts of suspended or mechanically carried solid matter, be increased if it is surrounded by an absorbent material, so that the emulsion is influenced by effects of the tube in the presence of an absorbentv The absorbent material functions also to extend the surface or elfective area of treatment of the emulsion. It preferably consists of pumice which has been suitably subdivided, but instead there maybe utilized other highly absorbent substances, as silica gel and like gels, absorbent trolytically, as copper, lead, cadmium, zinc, silver, and the like, in an amount of, for example, 0.1% of the weight of the absorbent.

Not only does the procedure occasion the resolution of an emulsion, but, in addition, effects a clarification due to the removal of suspended and colloidal particles; thus, a Water-oil emulsion, as a crude petroleum containing colloidal carbon, traces of metals, as iron, copper; iodine and salts, for example, magnesium chloride, sodium chloride, magnesium sulphate, and sodium sulphate, both as colloidal suspension in the oil and dissolved in the water forming the dispersed phase of the emulsion, may be readily and effectively treated with the result that the colloidal material is practically wholly removed and the emulsion resolved into its phases; or, in other words, the water containing dissolved salts removed.

As an illustrative embodiment of a manner in which the invention may be carried out in practise, the following example is presented:

A California crude oil accompanied by one to ninety per cent water and carrying in emulsified form from one to fifty per cent, most frequently ten-fifteen per cent, of water, colloidal carbon, traces of metal, and various salts, both as colloidal salts and dissolved in the water may be resolved into its phases by passing the oil in contact with a. hard type rare gas tube. For example, the tube may have a pressure of 10 mm.; be filled with 80% argon and 20% neon; and provided with iron electrodes, and operating at gbout 15 milliamperes under a voltage of about 12 0.

Contacting with the tube while under electrical impress and hence while the tube is vibrating strongly may be by positioning the tube within an enclosing jacket and surrounding by pumice stone upon which copper has been electrolytically deposited to the extent of 0.1% of the pumice and conducting the oil through the jacket and about the tube. sired, a plurality of tubes may be assembled within a single enclosing jacket, the spaces between the tubes being filled or not with the absorbent material as may be desirable and advisable and the emulsion passed through. The emulsion upon passing from the tube may be conducted to a suitable receptacle wherein the two phases, i. e., 011 and water, separate and may be individually withdrawn. The oil is thus freed from the water, colloidal material, and salts and may then be refined in the usual manner for the production therefrom of various fractions as gasoline, kerosene, fuel oil lubricants, etc. Separation of the oil from water, solid matters and/or accompanying gases may be augmented by subjecting the crude oil mass to centrifugal force either prior to or during passage over or about a gas tube. In addition, the gases with or without separation into various constituents may be returned to the oil following resolution of the emulsion, thus raising the gravity.

The foregoing procedure for the treatment of emulsions is of particular advantage inasmuch as thereby a substantially complete resolution of the emulsion may be accomplished. This is markedly desirable in connection with water-oil and oil-water type of emulsions and especially the emulsions encountered in the production of petroleum.v The method is applicable to all such emulsions regardless of the field in which they are produced and whether the base may be asphaltic, naphthenic, or parafilnic.

Specifically, emulsions that are particularly Furthermore, if de- 2, teases difficult to resolve or break have been found to be susceptible to resolution by the process described herein and especially such emulsions 'as are found in the producing fields along the Pacific Coast, for example, Long Beach, Signal Hill, and the like. It will be realized that the invention at its broad application is not limited to the treatment of petroleum emulsions, but likewise is adapted for the resolution of other emulsions, particularly of the water-oil type, as compositions containing shellac, glues, milk, and coating and impregnating compositions exemplified by paints and lacquers having a nitro cellulose, cellulose acetate, vinyl or other synthetic resin, or various ethers or esters of cellulose as the base materials.

A definite determination of the exact man ner in which emulsions are resolved by eifects emanating from an ionized gas tube has not been made, but it is believed that the separation is occasioned by a strong oscillatory action of the tube under the operating conditions; that is, with a relatively low amperage as 3-60 milliamperes and a relatively high voltage, e. g., 1200-15,000 volts. Further, it is deemed that the effect emanating from the tube is aided by the formation of ozone which contacts with the emulsion and assists in'the resolution. This effect may include or be augmented by various chemical actions in a measure perhaps marked by light or other rays arising within the tube and passing therefrom into the emulsion. Regardless of the correctness of this belief, it nevertheless has been found that emulsions may be very satisfactorily resolved by the above described procedure.

Since certain changes may be made in carrying out the above process without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention, which, as a matter of language, might be said to fall therebetween.

Having described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for the resolution of emulsions which comprises subjecting an emulsion to vibratory efiects emanating from a hard type, rare gas tube, said emulsion being in direct contact with said tube.

2. A process for the resolution of emulsions which comprises subjecting an emulsion to effects emanating from a positive column, hard type, rare gas tube, operating at 3 to milliamperes and under a voltage of from 1200 to 15,000, said emulsion being in direct contact with said tube. J

3. A process for the resolution of emulsions which comprises subjecting an emulsion to effects emanating from a hard type, rare gas tube containing about 80% argon and 20% neon; having a pressure of 10 mm.; being provided with iron electrodes, and operating at about 15 milliamperes and about 1200 volts, said emulsion beingin direct contact with said tube.

4. A process for the resolution of emulsions which comprises subjecting an emulsion to vibratory effects emanating from a. rare gas tube in the presence of an absorbent material, carrying a deposited metal. said emulsion being in 10 mm.. and provided with iron electrodes in direct contact with said tube. the presence of pumice carrying a deposit of cop- 5. A process for the resolution of emulsions per, said emulsion being in direct contact with which comprises subjecting an oil:water type of said tube.

5 emulsion to vibratory effects emanating from a '1. A process for the resolution of emulsions 5 hard type, rare gas tube, said emulsion being in which comprises subjecting an emulsion to efdirect contact with said tube. fects emanating from a positive column hard 6. A process for the resolution of emulsions type rare gas tube containing argon and neon which comprises subjecting an oilzwater type operating at three to sixty milliamperes and 10 of emulsion to vibratory effects emanating from under a voltage of 1200 to 15,000, said emulsion 10 a hard type, rare gas tube containing about 80% being in direct contact with said tube. argon and 20% neon; having a. pressure of WALDEMAR O. MITSCHERLING. 

